Preparation of mordant disazo-dyestuffs



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BAsEL, SWITZERLAND, 'F'IR'M irmmzmmn on MoRnAN'r nlsAzo-nins'roirnsDrawing; nmjuetitn. filed Jilly 2,;1s'26,-seria1.10. 120,251, and inGermany m 13,1925.

ve roundithat valuable mdrda t dis- L azo-dyestufl's can be obtained bysubjecting one amino group of parapl'ienylene diamlno sulphonic acid"aromatic 'para-diaminosulphonic acid compou'ndofi the benzene series) todiazoti'zation" and subsequent comv frbi atiQni With anaromaticgortho-hydrorry- 'carboxylic acid of the benzene series andconseQlitivelysubjeoting the secondajmino group thereoftp j furtherdiaZo'tiZation and comhim-ion; with an aromatic orthohydroziy- V'ca'rbo'xyli'c acid of'the benzene series. or For para-diamino-sulphonicI- acid compound of the benzene serieswhich, first, contains only onefree amino g'roup, while the other is substituted, forinstanceacetylated;

. {ree amine group'is ,diazotized, comb1I18'(1'W1tl1 one' molecule ofanearomatic orth0-hydr0XycarboXylic acid-of the benzene series; Inthefthus obtained'mono azo dyestiifi' th second amino group having beensubsti- 7 tuted; iii e." conife'rtedin'toa nonrdiaz'oti'zable 'state is'now reconi e rted into its dia'z qtiizable Sta e; for instance bysaponificauenu Then I fboxylioacid of the benzene series can vbe introduced twioeinto the dyest'uif 1 molecule.

' I But it is also possible to use two difierent' aromatic ore'sotinicacid, vmetacresotinio acid; pare alcetylatedi-i'n the well known "manner(see German specification N01? 129,000, r Exampleortho-hydroxycarboxylicacids, I (salicylioacid of the lbenzeneseries;ihom,o-

logues or derivatives thereof; suoh as ortho- 23 parts ofmonoacetyl-para-phenylene insoluble diazo body is filtered oft", and isstirred intoa solution containing 15' parts of 1 metacresotinic acid and15 parts of powdered sodiumcarbonate. The @eupun r mts 1111- medlatelyand is terminated after having slowly'added llparts of caustic soda lyeof 0 E'RNsrBonMERoF nsEL,'swiirzERLAnDQAssiGNoR T0 D'URANDkSz Uo-UENINs. or I The monoazo dyestuft which has separated V i in the formof'yellow crystals is filtered ofi',

then dissolved in water and 3040 parts of causticisoda lye;1the solutionis boiled for some Ytime in order tol'saponify the acetyl group; Thereremains then a reddish yellow solution ii hichis filtered andacidifiedfi The :dyestufi precipitates and is afterwards filt'ered;v":On'e" dissolves in sodium vcarbonate,

adds, the E necessary quantity of nitrite. and

acidifies ata low temperature while stirring;

well. I l l v c 1 e The insoluble d flZo body is filtered oifand stirredinto solution consisting of 14' parts of salicylic acidQl l parts ofcaustic. soda lye of 4;O 1B'. and QO'O Partsoi ice-water. "By iaddingQOparts of solid sodium carbonate the coupling is terminated. s Thebrownish orange reactlonmass inwlnch the formed dye stuff has partlyPIGClPltitt-Qd, s heated up,

filtered and froin'lthe filtered solution the product is saltedo-ut; v

I The reactions and the I acfesotihic acids .betwresor'cylic piacidc n Paraphenylenediaminosulphonic acidi of hth fi); I the const tution: I pfTheprocess' is illustrated bythe following l I I I I exa'mples part'sbeing p v. V i I 5 ,l I

' ",Paraphehylene, diamino'sulphonicaoid iis p "v s I l r l l U y NH;

7 products are illus ,tr'ated by the following formulae:

so I

v is transformedby acet' latiori' tomonoacetyl 9 Ipara-phenylenediaminesulphonic acid having probably the constitution:

NHa

.so nt l rnooonz which by diazotization of the free amino group andcoupling with metacresotinic acid yields an intermediate product of theconstitution H 1 Y NILOOOHa the latter giving by saponificationof theacetyl group, diazotization of the free amino group thus formed andcombination with 0 V 1 c v 7 1 This 'dyestufl dissolves 1n water givinga yelsalicylic acid'the dyestufi of the formula: i

low solution with'a red tone which turns into red with a'blue tone whensome caustic soda lye is added. The shade of the solution 0btained withconcentrated sulphuric acid is violet. If water is added tot-he latter,the dyestufl" precipitates in form otdark' brown flakes. r 1 7 Thenewdyestutf dyes chromed wool 'orange with a brown b01160" When printedwith a chromemordanton cotton it gives a strong orange shade with a"very fast.

red tone, ashade which is Example}! The amino-azo dyestuff i such as isobtained from acetylparaphenylenediamino sulphonic acid and salicylicacid in an analogousmanner to that indicated in Example I is diazotizedas described. This' dlazo compound obtained from 38.7 parts of thearnino-rzo-dyestuff is stirred into a mixture of 14 parts ofsalicyliciacid, 100 parts of water .7 and 25 par-ts of magnesiumcarbonate while cooling. A thick brownpaste results which is dilutedwith water, acidified and moderately warmed. The insoluble dyestuff isfiltered f and washed with diluted muriatic acid for "the purpose ofeliminating the magnesium salt. The dyestutf is finally disso'lvedinWa-' t-er and alkali, filteredand salted 'out. The. reactions vand theproducts are illustrated'by .the following formulae: iParaamino-sulphobenzeneazosalicylic acid obtained in an ortho-hydrolanalogous manner tothat indicated in E2; ample I and havingtllQCOIlStltUtlOIl c N: cooH' 7 NH S0311 OH gives by diazotizingthe freeamino group and coupling with salicylic acid the dyestuff of theconstitution: I g 7 H000 N=N V 011 I OH- N=i r coon c of thebenzene'series or containing two different aromatic 1ortho-hydroxycarboxvlic acids of the benzene series can be obtained,

lVhatlclaimis:

' r 1. The herein: described process for the manufacture of newmordantdisazo dyestuffs, consisting in starting from an arcmaticpara-diaminosulphonic acid compound of the benzene series,=-acylatingone of the amino groups of-said body toconv ert'it into anonediazotizable state, diazotizing the second" amino group of saidbodv'and'coupling the'diazo compound thus'obtain'ed with an aromatic vortho=hydroxycarboxylic acid of the benzene series, then reconvertingthe former amino group into its diazotizable state removing the. acylgroupby hydrolysis,

V diazotizing the thus reformed free amino group and furthercouplingwith an aromatic y carboxylickacid ofthe'benzene series;

i.ji'2'. Th'e manufacture of new mofrdant disazo-dyeher ein i describedprocess for. the

stuffs, consisting in starting from para-' phenylene diaminosulphonicacid, acylating one, of the amino groups of said body to conl vert itinto a non-diazotizable stat-e, diazotizing the second amino group ofsaid body and coupling the diazo compound thus obtained with an aromaticortho-hydroXycarboxylic acid of the benzene series, then 'reconvertingthe former amino group into its diazotizable state by removing the acylgroup by hydrolysis, diazotizingjthe thus re formed jfree amino groupand'further couplingwith an aromatic orthohydroxvcarboxylic acid of thebenzeneseriesk 3; The herein described processlfor the V manufactureofnew; mordant 'disazoz-dye- 0nd amino group of saidbody and coupling the:diazo compound thus obtained with sali-' 4 diaz'otizing the thus,re-formed free'amlno stuffs, consisting in starting from, a jam,

- diamino-sulphonic 'acid compound of the benzene series, acetylatingone of the two amino groups of said body to convert it into anon-diazotizable state, diazotizing the second amino group of said bodyand coupling I the diazocompound thus obtained with an aromaticortho-hydroxycarboxylic "acid of the benzene series, then 'reconve rtingthe former 211111110 group 1nto 1ts diazotlzable state by removingtheacetyl group by hydrolysis, diazotizing the thus; re formed freeamino-group andfurther coupling with an aromaticortho-hydroxycarboxylic'acid of the benzeneseries. v I 41 The hereindescribed manufacture of newmordant disazo-dyestuifs, consisting: instarting from paraphenylene diaminosulphonic," acid, acetylati ing oneof the two amino groupsof said body to convert it into anon-diazotizable state, diazotizing the second amino group of said 7body and coupling the diazo compound thus obtained with anaromaticortho-hydroxycarboxylic acid of the benzene series, thenreconverting the former amino groupinto its diazotizable state byremoving the acetyl v N N N=N w on process the corre'spond to thefollowing general formula:

S0311 i p whereinthe nuclei I, n and III besides the substituentsindicated in the formula may bear further substituents, vsaid mordantdis- In witness whereof I have hereunto signed my name this 21st day ofJune 1926. s ERNST BODMER.

group by hydrolysis, diazotizing the thus re-- o formed free amino groupand further coupling with an aromatic ortho-hydroxycar; i

, boxylicacid ofthe benzeneseries.

c 5., Theherein describedprocess for the manufacture of new 'mordantdisazo-dyestuffs, consisting in starting from a paradiamino-sulphonicacid compound "of the benzene series, acetylating one of" the two Vamino groups of said body to convert it into a non-diazotizable "state,'diazotizing the sec- 7 cylio acid, then reconverting the former amincgroup into its diazoti'zable state by removing the acetyl group I byhydrolysis, di'azotizing the thus: re-formed free amino 6. The hereindescribed process for the i group and furthercoupling with salicylic I"acid.x

manufacture of new fm ordantdisazo-dyestuffs, consisting in startingfromparaphenyleneadiaminosulphonic acid, acetylating one of the twoaminogroups of said body .to convert it into a non-diazotizable state,'diazotizing the second amino group of said body, and

. ccouplingthe diazo, compoundthus'obtained; f'with salicylic acid, then'reconverting the former. amino groupintoits diazotizable state byremoving the a'cetyl group by hydrolysis,

' group and further coupling with salicylic acid. 7 I 1 a a I J 7. Asnew articlesof manufacture the herein described mordantadisazordyestuffswhich

